The invention relates to a process for the preparation of compounds of the formula 
and, where appropriate, their tautomers, in each case in the free form or salt form, in which either
X is CH or N, Y is OR1 and Z is O, or
X is N, Y is NHR8 and Z is O, S or S(xe2x95x90O);
R1 is C1-C4alkyl;
R2 is H, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl or C1-C4alkoxymethyl;
R3 and R4 independently of one another are H, C1-C4alkyl, C1-C4alkoxy, OH, CN, NO2, a (C1-C4alkyl)3xe2x80x94Si group, where the alkyl groups can be identical or different, halogen, (C1-C4alkyl)S(xe2x95x90O)m, (halogeno-C1-C4alkyl)S(xe2x95x90O)m, halogeno-C1-C4alkyl or halogeno-C1-C4alkoxy;
R5 is C1-C6alkyl, halogeno-C1-C6alkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6-alkylthio, halogen-C1-C6alkylthio, C1-C6alkylsulfinyl, halogeno-C1-C6-alkylsulfinyl, C1-C6alkyl-sulfonyl, halogeno-C1-C6alkylsulfonyl, C1-C6alkoxy-C1-C6alkyl, halogeno-C1-C6alkoxy-C1-C6alkyl, C1-C6alkylthio-C1-C6alkyl, halogeno-C1-C6alkylthio-C1-C6alkyl, C1-C6alky sulfinyl-C1-C6alkyl, halogeno-C1-C6-alkylsulfinyl-C1-C6alkyl, C1-C6-alkylsulfonyl-C1-C6alkyl, halogeno-C1-C6-alkylsulfonyl-C1-C6alkyl, C1-C6-alkylcarbonyl, halogeno-C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, halogeno-C1-C6-alkoxycarbonyl, C1-C6-alkyl-aminocarbonyl, C1-C4-alkoxyiminomethyl; di(C1-C6alkyl)-aminocarbonyl, where the alkyl groups can be identical or different; C1-C6-alkylaminothiocarbonyl; di(C1-C6alkyl)-aminothiocarbonyl, where the alkyl groups can be identical or different; C1-C6-alkyl-amino, di(C1-C6alkyl)-amino, where the alkyl groups can be identical or different; halogen, NO2, CN, SF5, thioamido, thiocyanatomethyl; an unsubstituted or mono- to tetrasubstituted C1-C4alkylenedioxy group, where the substituents are selected from the group consisting of C1-C4alkyl and halogen; or QR6, where, if n is greater than 1, the radicals R5 can be identical or different;
R6 is C2-C6alkenyl or C2-C6 alkynyl which are unsubstituted or substituted by 1 to 3 halogen atoms; (C1-C4alkyl)3Si, where the alkyl groups can be identical or different; CN; or an unsubstituted or mono- to pentasubstituted C3-C6cycloalkyl, aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, phenoxy, naphthoxy and CN;
A either is a direct bond, C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and R7 is a radical R10, or is C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and R7 is OR10, N(R10)2, where the radicals R10 can be identical or different, or xe2x80x94S(xe2x95x90O)qR10; 
R8 is H or C1-C4alkyl;
R9 is methyl, fluoromethyl or difluoromethyl;
R10 is H; an unsubstituted or substituted C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl group, where the substituents are selected from the group consisting of halogen; (C1-C4alkyl)3Si, where the alkyl groups can be identical or different; C3-C6cyclo-alkyl, which is unsubstituted or substituted by halogen; C1-C6alkoxycarbonyl, which is unsubstituted or substituted by halogen; unsubstituted or substituted aryl, where the substituents are selected from the group consisting of halogen, halogeno-C1-C4alkyl and CN; a (C1-C4alkyl)3Si group, where the alkyl groups can be identical or different; C3-C6cycloalkyl, which is unsubstituted or substituted by halogen; C1-C6alkoxycarbonyl which is unsubstituted or substituted by halogen; or an unsubstituted or substituted aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen and halogeno-C1-C4alkyl;
Q is a direct bond, C1-C8alkylene, C2-C6alkenylene, C2-C6alkynylene, O, O(C1-C6alkylene), (C1-C6alkylene)O, S(xe2x95x90O)p, S(xe2x95x90O)p(C1-C6alkylene) or (C1-C6alkylene)S(xe2x95x90O)p;
m is 0, 1 or 2;
n is 0, 1, 2, 3, 4 or 5;
p is 0, 1 or 2; and
q is 0, 1 or 2,
and the Cxe2x95x90N double bond marked with E has the E configuration,
which comprises
a1) reacting either a compound of the formula 
xe2x80x83in which A, R2, R5, R7 and n are as defined for formula I and the Cxe2x95x90N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a compound of the formula 
xe2x80x83which is known or can be prepared by methods known per se and
in which X, Y, Z, R3, R4 and R9 are as defined for formula I and X1 is a leaving group, or a tautomer thereof, in each case in the free from or in salt form, or
a2) reacting a compound of the formula 
xe2x80x83in which A, R2, R5, R7 and n are as defined for formula I and the Cxe2x95x90N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in the salt form, if appropriate in the presence of a base, with a compound of the formula 
xe2x80x83which is known or can be prepared by methods known per se and
in which X, Y, Z, R3, R4 and R9 are as defined for formula I, or a tautomer thereof, in each case in the free form or in salt form, or
b1) reacting a compound of the formula 
xe2x80x83in which A, R2, R5 and n are as defined for formula I and the Cxe2x95x90N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a compound of the formula
R7xe2x80x94Axe2x80x94X2xe2x80x83xe2x80x83(VII),
xe2x80x83which is known or can be prepared by methods known per se and
in which A and R7 are as defined for formula I and X2 is a leaving group, and either further reacting the compound thus obtainable, of the formula IV, for example according to method a1), or
b2) reacting it with hydroxylamine or a salt thereof, if appropriate in the presence of a base or acid catalyst, and further reacting the compound thus obtainable, of the formula II, for example according to method a1), or
c) reacting a compound of the formula 
xe2x80x83which is known or can be prepared by methods known per se and
in which R2, R5 and n are as defined for formula I, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a C1-C6alkyl nitrite, and further reacting the compound thus obtainable, of the formula VI, for example according to method b),
the E isomers of the compounds of the formulae II, IV and VI, or a tautomer thereof, in each case in the free form or in salt form, a process for their preparation and their use for the preparation of compounds of the formula I.
The compounds of the formula I are known pesticides. The processes known to date for their preparation give mixtures of E and Z isomers in respect of the Cxe2x95x90N double bond marked with E in formula I of different composition, depending on the process. Since the biological properties of the E isomers are in each case found to be superior to those of the mixtures and of the Z isomers, there is a need to develop preparation processes for compounds of the formula I having the isomerically pure E configuration. This object is achieved by the preparation process according to the invention.
Unless defined differently, the general terms used above and below are defined as follows.
Carbon-containing groups and compounds in each case contain 1 up to and including 8, preferably 1 up to and including 6, in particular 1 up to and including 4, especially 1 or 2, carbon atoms.
Alkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, halogenoalkoxycarbonyl, alkylaminocarbonyl, alkoxyiminomethyl, alkylaminothiocarbonyl and alkylaminoxe2x80x94is, in each case taking into due consideration the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkenylxe2x80x94is, in each case under due consideration of the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, for example vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example iso-propenyl.
Alkynylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkynylxe2x80x94is, in each case under due consideration of the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl.
C3-C6cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkylenexe2x80x94as a group per se and as a structural element of other groups and compounds, such as of O(alkylene), (alkylene)O, S(xe2x95x90O)p(alkylene), (alkylene)S(xe2x95x90O)p or alkylenedioxyxe2x80x94is, in each case under due consideration of the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, for example xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94or xe2x80x94CH2CH2CH2CH2xe2x80x94, or branched, for example xe2x80x94CH(CH3)xe2x80x94, xe2x80x94CH(C2H5)xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94 or xe2x80x94CH(CH3)CH(CH3)xe2x80x94.
Alkenylene is, in each case under due consideration of the number, from case to case, of carbon atoms contained in the corresponding compound, either straight-chain, for example vin-1,2-ylene, all-1,3-ylene, but-1-en-1,4-ylene or hex-2-en-1,6-ylene, or branched, for example 1-methylvin-1,2-ylene.
Alkynylene is, in each case under due consideration of the number, from case to case, of carbon atoms contained in the corresponding compound, either straight-chain, for example propargylene, 2-butynylene or 5-hexynylene, or branched, for example 2-ethynylpropylene or 2-propargylisopropylene.
Aryl is phenyl or naphthyl, in particular phenyl.
Heterocyclyl is a 5- to 7-membered aromatic or non-aromatic ring having one to three heteroatoms, which are selected from the group consisting of N, O and S. 5- and 6-membered rings which contain a nitrogen atom as a heteroatom and, if appropriate, a further heteroatom, preferably nitrogen or sulfur, in particular nitrogen, are preferred.
Halogenxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkyl, halogenoalkenyl and halogenoalkynylxe2x80x94is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, in particular fluorine or chlorine, very especially fluorine.
Halogen-substituted carbon-containing groups and compounds, such as halogenoalkyl, halogenoalkenyl or halogenoalkynyl, can be partly halogenated or perhalogenated, and in the case of polyhalogenation, the halogen substituents can be identical or different. Examples of halogenoalkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkenylxe2x80x94are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CFCl2, CF2CHBr2, CF2CHClF, CF2CHBrF or CClFCHClF; propyl or isopropyl which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; and butyl or one of its isomers which is mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF3)-CHFCF3or CH2(CF2)2CF3. Halogenoalkenyl is, for example, CH2CHxe2x95x90CHCl, CH2CHxe2x95x90CCl2, CH2CFxe2x95x90CF2 or CH2CHxe2x95x90CHCH2Br. Halogenoalkynyl is, for example, CH2Cxe2x89xa1CF, CH2Cxe2x89xa1CCH2Cl or CF2CF2Cxe2x89xa1CCH2F.
Some compounds I to VI and VII can be present as tautomers, as is familiar to the expert, in particular if AR7 is H. Compounds I above and below are therefore also to be understood as meaning corresponding tautomers, even if the latter are not mentioned specifically in each case.
Compounds I to VI and VII which contain at least one basic centre, can form, for example, acid addition salts. These are formed, for example, with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid, or a hydrogen halide acid, with strong inorganic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as dicarboxylic acids which are saturated or unsaturated, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds I with at least one acid group can furthermore form salts with bases. Suitable salts with bases are, for example, metal salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. Furthermore, where appropriate, corresponding inner salts can be formed. Agrochemically advantageous salts are preferred in the context of the invention; however, salts which have disadvantages for agrochemical uses, for example salts which are toxic to bees or fish, which are employed, for example, for isolation or purification of free compounds I or agrochemically usable salts thereof, are also included. Compounds of the formulae I to VI and VII in the free form and in the form of their salts are also to be understood above and below as meaning the corresponding salts or the free compounds I to VI and VII. The same applies to tautomers of compounds of the formulae I to VI and VII and salts thereof. In general, the free form is in each case preferred.
The reactions described above and below are carried out in a manner known per se, for example in the absence or usually in the presence of a suitable solvent or diluent or a mixture thereof, the reaction being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range from about xe2x88x9280xc2x0 C. up to the boiling point of the reaction medium, preferably from about 0xc2x0 C. up to about 150xc2x0 C., and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Particularly advantageous reaction conditions can be seen from the examples.
The starting materials mentioned above and below, which are used for the preparation of the compounds I, in each case in the free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the following statements.
Suitable leaving groups X1 in compounds III are, for example, hydroxyl, C1-C8alkoxy, halogeno-C1-C8alkoxy, C1-C8alkanoyloxy, mercapto, C1-C8alkylthio, halogeno-C1-C8alkylthio, C1-C8alkanesulfonyloxy, halogeno-C1-C8alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen, in particular halogen.
Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, N-alkylated or non-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammonium hydroxides and carbocyclic amines. Examples are sodium hydroxide, hydride, amide, methanolate, acetate and carbonate, potassium tert-butanolate, hydroxide, carbonate, and hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropyl-ethyl-amine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethyl-amine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyl-trimethyl-ammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or of a mixture thereof is usually advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenohydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve as the solvent or diluent.
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. up to about 180xc2x0 C., preferably from about 10xc2x0 C. up to about 80xc2x0 C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; preferably, however, it is carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
In a preferred embodiment of variants a1/a2), a compound II is reacted with a compound III at 0xc2x0 C. to 80xc2x0 C., preferably 10xc2x0 C. to 30xc2x0 C., in an inert solvent, preferably an amide, in particular N,N-dimethyiformamide in the presence of a metal hydride, preferably sodium hydride.
Particularly preferred conditions for the reaction are described in Examples H1d) and H3f).
The compounds of the formula III are known or can be prepared analogously to known compounds. The compounds I are known. However, their preparation according to the prior art has a large number of serious industrial, ecological, economic and other disadvantages.
Thus, in the preparation processes according to the prior art, as a rule E/Z isomer mixtures with respect to the Cxe2x95x90N double bond marked with E in formula I are obtained. Since the biological properties of the E isomers are in each case found to be superior to those of the mixtures and of the Z isomers in each case, the processes according to the prior art have the significant disadvantage that products are produced which are either significantly less active as E/Z mixtures or from which the Z isomers must be removed in order to increase their biological activity, which means that many unnecessary handling operations must be carried out for separation of isomers, which has the effect of being very time-consuming, blocks valuable production lines for a long time and is associated with high additional energy costs. The removal of the less active Z isomer also leads to additional enormous losses in yield, which in turn not only is problematic and ecologically disadvantageous, but also renders the process according to the prior art much more expensive and consequently economically of no interest. The industrial, ecological, economic and other disadvantages of the processes according to the prior art are not limited to those described above, these latter being intended to serve only as a few examples of the large number of disadvantages of the processes according to the prior art. The disadvantages of the processes according to the prior art cause serious problems even when the processes are carried out on a laboratory scale. When the processes are carried out on a larger scale, these disadvantages intensify considerably. In the end, however, the aim is to carry out a specific process on an industrial scale if this process is to be suitable for preparing products for agrochemical purposes.
According to the process of the present invention, the compounds I are prepared by reaction of the compound II with a compound III or by reaction of the compound IV with a compound V. These processes according to the invention have extremely surprising industrial, ecological, economic and other advantages compared with the processes from the prior art. Since the compounds II or, respectively, IV are present in the preparation process according to the invention as pure E isomers in respect of the Cxe2x95x90N double bond marked with E, only the E isomer of the compounds I is produced in the present process, which has the effect of an enormous saving in time and at the same time a high saving in cost and energy, since no valuable production lines are blocked for a long time for separation of the isomers, and at the same time the amount of biologically more active E isomer produced by per unit time is much higher than in the processes according to the prior art. The resources such as starting products and energy are consequently utilized to the optimum in the present process, which not only very greatly simplifies the process and renders it ecologically advantageous, but consequently renders it cheaper and therefore of greater economic interest. This means that all the disadvantages of the processes according to the prior art which can be attributed to the formation of E/Z isomers are avoided. The industrial, ecological, economic and other advantages of the process according to the invention are not limited only to those described above, these latter being intended to serve only as a few examples of the large number of advantages inherent in this process. Due to all the abovementioned advantages of the present process, the serious problems which occur in the processes according to the prior art are avoided even at the stage of a laboratory process. If the present process is used on a larger scale, these advantages prove to be even much more significant, which has the effect that these advantages first allow the process to be used on an industrial scale.
For this reason, all the industrial, ecological, economic and other disadvantages of the processes according to the prior art are surprisingly advantageously overcome in the preparation of compounds I by the present process.
The process according to variant b) is carried out by first reacting compound VI with compound VII, if appropriate further reacting the resulting product IV, if appropriate after isolation, with hydroxylamine or a salt thereof, and further reacting the resulting products II or, respectively, IV, if appropriate after isolation, in accordance with variants a1/a2), for example in the manner described above, to give the compounds I.
Suitable leaving groups X2 in the compounds VII are, for example, those which are mentioned as examples for X1 in variants a1/a2).
Suitable bases for facilitating the reaction are, for example, those which are mentioned in variants a1/a2).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or of a mixture thereof is usually advantageous. Examples of such solvents or diluents are those mentioned in variants a1/a2).
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about 180xc2x0 C., preferably from about 10xc2x0 C. to about 80xc2x0 C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; preferably, however, it is carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 5 hours, is preferred.
The product is isolated by customary methods, for example filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
In a preferred embodiment of variant b), a compound VI is reacted with a compound VII at 0xc2x0 C. to 80xc2x0 C., preferably 10xc2x0 C. to 60xc2x0 C., in an inert solvent, preferably a nitrile, in particular acetonitrile, in the presence of a metal carbonate, preferably potassium carbonate, and the compound IV thus obtainable is then further reacted, preferably in accordance with method a2).
Particularly preferred conditions for the reaction are described in Examples H 1 b) to 1 d) and H 3d) to 3f).
The compounds of the formula VII are known or can be prepared analogously to known compounds.
The present process according to the invention of variant b), which in principle is an advantageous combination of an O-alkylation reaction with process variants a1/a2) according to the invention, has all the great advantages compared with the prior art which have already been discussed above for the process according to the invention of variants a1/a2). In particular, the process of variant b) ensures that the E configuration of the Cxe2x95x90N double bond marked with E in compound VI is retained. Furthermore, however, the process according to the invention of variant b) also has further industrial, ecological, economic and other advantages which are connected with the specific property that the intermediate product IV initially formed is not purified but is directly further processed as the moist crude product, in the case of intermediate isolation, or in situ in the reaction mixture, if it is not isolated. This missing purification step on the intermediate product mentioned is of advantage, for example, in as much as it is not necessary to dry it, which not only saves energy and further resources, but also enormously increases the safety of the preparation process, since the possible danger of a dust explosion of the dry intermediate product is averted completely. The savings in resources are even greater if the intermediate product is further reacted without purification, since, for example, no additional solvents are consumed for the recrystallization. The process of variant b) is of particular advantage compared with the individual process steps of the alkylation reaction of variants a1/a2) carried out in that the total reaction time in the process of variant b) is much shorter, which consequently leads to a much higher production of reaction product I per unit time and therefore to a much more efficient utilization of the valuable production lines. Furthermore, the total yield of reaction product I is surprisingly good when the process of variant b) is employed, and, compared with the combined yields of the individual process steps of the alkylation reaction and variants a1/a2) carried out, is in the same percentage range or even better. The industrial, ecological, economic and other advantages of the process according to the invention of variant b) are not limited to those described above, these latter being intended to serve only as a few examples of the large number of advantages inherent in the process according to the invention of variant b).
By using process variant b) according to the invention for preparation of the compounds I, a large number of industrial, ecological, economic and other advantages can therefore surprisingly be utilized efficiently.
The process according to variant c) is carried out by first reacting compound VII with an alkylnitrite and further reacting the resulting product VI, if appropriate after isolation, in accordance with variant b), for example in the manner described above, to give the compounds I.
Suitable bases for facilitating the reaction are, for example, those which are mentioned in variants a1/a2).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or of a mixture thereof is usually advantageous. Examples of such solvents or diluents are those mentioned in variants a1/a2).
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about 180xc2x0 C., preferably from about 0xc2x0 C. to about 60xc2x0 C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; preferably, however, it is carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 3 hours, is preferred.
The product is isolated by customary methods, for example filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
In a preferred embodiment of variant c), a compound VII is reacted with an alkyl nitrite at 0xc2x0 C. to 80xc2x0 C., preferably 0xc2x0 C. to 40xc2x0 C., in an inert solvent, preferably an alcohol, in particular methanol, in the presence of a metal alcoholate, preferably sodium methanolate, and the compound VI thus obtainable is then further reacted, preferably in accordance with method b).
Particularly preferred conditions for the reactions are described in Examples H 3d) to 3f).
The compounds of the formula VII are known or can be prepared analogously to known compounds.
The present process according to the invention of variant c), which in principle is an advantageous combination of an oximation reaction with process variants a1/a2) and b) according to the invention, has all the great advantages compared with the prior art which have already been discussed above for the processes according to the invention of variants a1/a2) and b). Furthermore, the present oximation process for the preparation of the compounds VI surprisingly result exclusively in the E configuration of the Cxe2x95x90N double bond marked with E in formula VI. It is thus ensured that the particular starting products II, IV or, respectively, VI in the subsequent processes according to the invention for the preparation of the compounds I, for example in process variants a1/a2) and b), are pure E isomers.
A large number of industrial, ecological, economic and other advantages can therefore surprisingly be utilized efficiently by using process variants c) according to the invention for the preparation of the compounds of the formula I.
The E isomers of the compounds of the formulae II, IV and VI and tautomers thereof, in each case in the free form or in salt form, are novel and the present invention likewise relates to them.
The present invention furthermore relates to a process for the preparation of the E isomers of a compound of the formula VI or of a tautomer thereof, in each case in the free form or in salt form, according to the abovementioned process c),
a process for the preparation of the E isomers of a compound of the formula IV, or of a tautomer thereof, in each case in the free form or in salt form, according to the abovementioned process b1), and
a process for the preparation of the E isomers of a compound of the formula II, or of a tautomer thereof, in each case in the free form or in salt form, according to the abovementioned process b2).
The process conditions for the preparation of these intermediate products can be seen from the abovementioned processes a), b) and c).